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US7842648B2 - Aqueous suspended agricultural chemical composition - Google Patents

Aqueous suspended agricultural chemical composition Download PDF

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Publication number
US7842648B2
US7842648B2 US12/149,777 US14977708A US7842648B2 US 7842648 B2 US7842648 B2 US 7842648B2 US 14977708 A US14977708 A US 14977708A US 7842648 B2 US7842648 B2 US 7842648B2
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US
United States
Prior art keywords
general name
ethyl
yloxy
phenoxy
propionate
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Expired - Fee Related, expires
Application number
US12/149,777
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US20080220975A1 (en
Inventor
Katsushi Shio
Shoji Suzuki
Naoki Matsumoto
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Nissan Chemical Corp
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Nissan Chemical Corp
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Publication date
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Priority to US12/149,777 priority Critical patent/US7842648B2/en
Publication of US20080220975A1 publication Critical patent/US20080220975A1/en
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Publication of US7842648B2 publication Critical patent/US7842648B2/en
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines

Definitions

  • the present invention relates to an aqueous suspended agricultural chemical composition having high preservation stability, which contains ethyl(R)-2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionate.
  • Ethyl(R)-2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionate (hereinafter referred to as quizalofop-p-ethyl) is known to have two kinds of crystal forms.
  • One is a low melting point type crystal (hereinafter referred to as ⁇ -type crystal) and the other is a high melting point type crystal (hereinafter referred to as ⁇ -type crystal) (see Japanese Patent Examined Publication No. Hei 4-76721).
  • An aqueous suspended agricultural chemical composition containing the following components (a), (b), and (c).
  • aqueous suspended agricultural chemical composition as described in the above item [1] to [3], wherein the component (a) is 1 to 60 parts by weight, the component (b) is 0.1 to 60 parts by weight, and the component (c) is 20 to 95 parts by weight, respectively, based on 100 parts by weight of the aqueous suspended composition.
  • the ratio of ⁇ -type crystal is at least 80% by weight or more, preferably 85% by weight or more, and more preferably 90% by weight or more in terms of the preservation stability of the agricultural chemical composition. If the ratio of ⁇ -type crystal is less than 80 wt %, the particle size of quizalofop-p-ethyl particle in the aqueous suspended agricultural chemical composition may increase (hereinafter referred to as particle growth) or flowability of the composition may deteriorate by storing the composition under severe condition such as at 50° C. for 30 days. The particle growth is not preferred in terms of herbicide effect and deteriorated flowability is not preferred in terms of the convenience of handling.
  • Quizalofop-p-ethyl is known to have two kinds of crystal forms.
  • One is ⁇ -type crystal (low melting point type crystal), a plate crystal, of which endothermal peak is around 74° C. in differential scanning calorimetry, and the other is ⁇ -type crystal (high melting point type crystal), needle crystal, which endothermal peak is around 80° C.
  • the weight ratio of ⁇ -type crystal to ⁇ -type crystal approximates to the area ratio of each endothermal peak in the differential scanning calorimetry, the weight ratio of ⁇ -type crystal to ⁇ -type crystal is obtained from the area ratio of the respective endothermal peaks.
  • the method of obtaining quizalofop-p-ethyl, in which the ratio of ⁇ -crystal is 80% by weight or more, is not specifically limited.
  • a method described in Japanese Patent Examined Publication No. Hei 4-76721 is suitably used in this invention. According to this method, quizalofop-p-ethyl containing ⁇ -type crystal at any ratio can be obtained.
  • quizalofop-p-ethyl may be replaced with diphenyl ether herbicide such as propaquizafop (general name), quizalofop-p-tefuryl (general name), fenoxaprop-ethyl (general name) in the invention.
  • diphenyl ether herbicide such as propaquizafop (general name), quizalofop-p-tefuryl (general name), fenoxaprop-ethyl (general name) in the invention.
  • ⁇ -type crystal means high melting point type crystal
  • ⁇ -type crystal means low melting point type crystal.
  • Usable surfactant is not specifically limited and various anionic surfactants and nonionic surfactants heretofore used in agricultural chemical field are suitably used in the invention. Examples of surfactants are listed hereinafter. However surfactants suitably used in the invention are not limited to those listed therein.
  • anionic surfactants which can be suitably used in the invention include sulfonic acid surfactants, sulfate surfactants, phosphate surfactants and their salts.
  • suitable sulfonic acid surfactants are alkylsulfonic acid, alkylolefinsulfonic acid, lignosulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, naphthalenesulfonic acid formaldehyde condensate, and dialkylsulfosuccinate.
  • Suitable sulfate surfactants are polyoxyethylene alkylether sulfate, polyoxyethylene alkylallylether sulfate, polyoxyethylene styrylphenylether sulfate, polyoxyethylene phenylalkylallylether sulfate, polyoxyalkylene glycol sulfate, higher alcohol sulfate, and fatty acid ester sulfate.
  • suitable phosphate surfactants are polyoxyethylene alkylether phosphate, polyoxyethylene alkylallyl phosphate, polyoxyethylene phenylalkylallylether phosphate, higher alcohol phosphate, and polyoxyethylene tribenzylphenol phosphate.
  • salts are sodium-, potassium-, magnesium-, calcium-, ammonium-, ethanolamine-, diethanolamine- and triethanol amine-salt.
  • nonionic surfactants are polyoxyethylene alkylallyether, polyoxyethylene styrylphenylether, polyoxyethylene alkylether, polyoxyethylene phenylalkylallylether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycol, polyoxyethylene polyoxypropylene block co-polymer, polyoxyalkylene glycol, alkyne diol (acetylene glycol), alkynylene polyoxyethylenediol, sorbitan fatty acid ester and alkylallylether formaldehyde condensate and so forth.
  • surfactants can be used separately or two kinds or more surfactants are allowed to be mixed.
  • the mixing ratio can be freely selected.
  • content of quizalofop-p-ethyl in which the ratio of ⁇ -type crystal is 80% by weight or more is not specifically limited, however it is generally 1 to 60 parts by weight, preferably 3 to 50 parts by weight to 100 parts by weight of the composition.
  • Content of the surfactant is generally 0.1 to 60 parts by weight, preferably 0.3 to 50 parts by weight.
  • Content of water is generally 20 to 95 parts by weight.
  • composition of the invention can further contain following active components of agricultural chemicals.
  • Examples of the active components of agricultural chemicals suitably used in the invention include Diflufenican (general name), Propanil (general name), Dicamba (general name), Picloram (general name), 2,4-D (general name), 2,4-DB (general name), 2,4-DP (general name), Fluoroxypyr (general name), MCPA (general name), MCPP (general name), Triclopyr (general name), Diclofop-methyl (general name), Fenoxaprop-ethyl (general name), Fluazifop-butyl (general name), Haloxyfop-methyl (general name), Chloridazon (general name), Norflurazon (general name), Chlorpropham (general name), Desmedipham (general name), Phenmedipham (general name), Propham (general name), Alachlor (general name), Acetochlor (general name), Butachlor (general name), Metazachlor (general name), Metolachlor (general name), Pretilachlor (general name), Propachlor (general name), Ory
  • active components of agricultural chemicals are used separately or two kinds or more of them are allowed to be mixed.
  • the mixing rate can be freely selected.
  • the amount of addition of the active components to the composition of the invention is properly selected. However, preferably, it is selected within 0.1 to 50 parts by weight.
  • Adjuvants suitably contained in the composition of this invention include thickeners, antifreezing agents, antifoaming agents, antibacterial and antifungal agents, and colorants, and the examples are cited as follows.
  • Thickeners suitably used in the composition of this invention are not specifically limited and include organic- and inorganic-natural materials and synthetic- and semisynthetic products.
  • the thickeners suitably used in the invention include heteropolysaccharides, water soluble polymer compounds, cellulose derivatives, and smectite clay minerals.
  • suitable heteropolysaccharides are xanthan gum, welan gum and rhamxan gum.
  • suitable water soluble polymer compounds are polyvinylalcohol, polyvinylpyrrolidone, polyacrylic acid, sodium poly acrylate, and polyacrylamide.
  • Suitable cellulose derivatives are methylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.
  • suitable smectite clay minerals are montmorillonite, saponite, hectorite, bentonite, raponite and synthetic smectite. These thickeners can be used separately or two kinds or more of them can be mixed and the ratio of the mixing can be selected freely.
  • Intact thickeners or those dispersed in water beforehand are allowed to be added. And the amount of the addition can be selected freely at its addition to the component of the invention.
  • Antifreezing agents may be used in the composition of this invention if required.
  • As usable antifreezing agents there may be added ethylene glycol, diethylene glycol, propylene glycol, or the like. The amount of the addition is freely selected at its addition to the composition of this invention.
  • antifoaming agent such as silicon emulsion, antibacterial and antifungal agents, and colorants are allowed to be blended.
  • Various antibacterial and antifungal agents may be used in the invention.
  • suitable antibacterial and antifungal agents include benzoic acid and its salt, Proxel GXL (ICI Corp.) and Proxel XL-2 (ICI Corp.).
  • suitable antibacterial and antifungal agents include benzoic acid and its salt, Proxel GXL (ICI Corp.) and Proxel XL-2 (ICI Corp.).
  • proper selection is made from various antibacterial and antifungal agents.
  • the amounts of addition can be freely selected at their addition to the composition of the invention.
  • composition of the invention is, for example, prepared by a method in which the solid components contained in the composition of the invention is mixed into the water added and mixed with a surfactant, and then the mixture is subjected to atomization with a wet mill such as a sand grinder, and then, to the atomized mixture, other adjuvants such as a thickener is added and mixed.
  • a surfactant such as a sand grinder
  • Vangel smectite clay mineral/thickener/R.T. VANDERBILT Corp., Product name
  • 0.14 parts of xanthan gum 0.14 parts of Proxycel GXL (ICI Corp., Product name) were dispersed in 67.48 parts of water in order of Vangel, xanthan gum and Proxycel GXL.
  • 30 parts of propylene glycol is added therein to obtain a dispersion medium.
  • the above-mentioned ground slurry was mixed in the dispersion medium in the ratio of two to one to obtain a homogeneous aqueous suspended agricultural chemical composition.
  • aqueous suspended agricultural chemical composition From the obtained aqueous suspended agricultural chemical composition, about 3 g of the composition was separated, and then it was suspended in about 60 ml of water. Then the suspension was subjected to a centrifugal separator (Kokusan Enshinki Corp., H-300 type, at 3,000 rpm for 15 minutes) and the formed supernatant was removed. Then the obtained precipitation was suspended in about 60 ml of water and subjected to the centrifugal separator again. This washing operation with water was repeated six times. The obtained precipitation was spread on a filter paper and then dried in a desiccator for about 20 hours. Then 3 to 5 mg of the dried material was weighed accurately and subjected to differential scanning calorimetry (Mac Science Corp.
  • Example 1 aqueous suspensions of agricultural chemical composition, in which the ratio of ⁇ -type crystal in quizalofop-p-ethyl is 80% by weight or more, were obtained (Example 2: 96 wt %, Example 3: 90 wt %, Example 4: 85 wt %, Example 5: 80 wt %).
  • Example 1 was repeated using quizalofop-p-ethyl (ratio of ⁇ -type crystal:100% by weight) except that 4.5 parts of Soprophor FL (polyoxyethylene tristyrylphenylether phosphate/RHONE-POULENC Corp., Product name) was used in stead of 4.5 parts of Sorpol 3353 to prepare an aqueous suspended agricultural chemical composition.
  • Soprophor FL polyoxyethylene tristyrylphenylether phosphate/RHONE-POULENC Corp., Product name
  • Ratio of ⁇ -type crystal in quizalofop-p-ethyl was 100% by weight in the obtained aqueous suspended agricultural chemical composition.
  • the above-mentioned ground slurry and dispersion medium were mixed in the ratio of 4 to 1 to obtain a homogeneous aqueous suspended agricultural chemical composition.
  • the rate of ⁇ -type crystal in quizalofop-p-ethyl was 100% by weight in the obtained aqueous suspended agricultural chemical composition.
  • Example 7 an aqueous suspended agricultural chemical composition was obtained, in which a ratio of ⁇ -type crystal of quizalofop-p-ethyl was 96% by weight.
  • the above-mentioned ground slurry and dispersion medium was mixed in the ratio of 9 to 1 to obtain a homogeneous aqueous suspended agricultural chemical composition.
  • Ratio of ⁇ -type crystal of quizalofop-p-ethyl is 100% by weight in the obtained aqueous suspended agricultural chemical composition.
  • Example 1 an aqueous mixture of agricultural chemical composition was obtained, in which ratio of ⁇ -type crystal in quizalofop-p-ethyl was less than 80% by weight (Comparative Example 1: 78 wt %, Comparative Example 2: 38 wt %, Comparative Example 3: 10 wt %, Comparative Example 4: 0 wt %).
  • Particle size and viscosity of the aqueous suspended agricultural chemical composition obtained in Example 1 to 9, and in Comparative Example 1 to 4 were measured. Further, after they had been put in vials (inside volume 50 ml) respectively and stored in thermostatic chamber at 50° C. for 30 days, the particle size were measured.
  • volume medium diameter (d50) values ( ⁇ m) of the particles were measured with a Laser Diffraction Technique Particle Size Analyzer LS-130 (Coulter Corp.) using garnet. omd as an optical model.
  • the viscosity was measured with a Viscometer DV-III (Brookfield Corp.) using No. 2 rotor at 30 rpm and 25° C.
  • Table 1 shows the result.
  • the symbols in the Table have the following meanings.
  • B Volume medium diameter ( ⁇ -m) of quizalofop-p-ethyl particle in the aqueous suspended composition immediately after preparation.
  • Example 1 100 1.3 180 1.9 248 Example 2 96 1.4 213 1.8 321 Example 3 90 1.2 167 2.0 252 Example 4 85 1.3 216 2.2 279 Example 5 80 1.3 193 2.4 332 Example 6 100 1.1 178 1.6 232 Example 7 100 1.0 202 1.7 185 Example 8 96 1.2 227 1.6 178 Example 9 100 1.3 451 2.1 337 Comparison 1 78 1.2 178 4.3 >1000 Comparison 2 38 1.4 201 5.8 >1000 Comparison 3 10 1.1 194 4.9 >1000 Comparison 4 0 1.2 225 5.2 >1000
  • D and E show properties after 30 days storage at 50° C.
  • An aqueous suspended agriculture chemical composition in the invention maintains good flowability and the growth of the quizalofop-p-ethyl particle is small, resulting in high preservation stability of the compositions under severe preservation condition.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US12/149,777 1997-07-11 2008-05-08 Aqueous suspended agricultural chemical composition Expired - Fee Related US7842648B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/149,777 US7842648B2 (en) 1997-07-11 2008-05-08 Aqueous suspended agricultural chemical composition

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP9-186553 1997-07-11
JP18655397 1997-07-11
JP11845798 1998-04-28
JP10-118457 1998-04-28
PCT/JP1998/002500 WO1999002036A1 (fr) 1997-07-11 1998-06-05 Composition pesticide de type suspension aqueuse
US44673099A 1999-12-27 1999-12-27
US12/149,777 US7842648B2 (en) 1997-07-11 2008-05-08 Aqueous suspended agricultural chemical composition

Related Parent Applications (3)

Application Number Title Priority Date Filing Date
US09446730 Continuation 1998-06-05
PCT/JP1998/002500 Continuation WO1999002036A1 (fr) 1997-07-11 1998-06-05 Composition pesticide de type suspension aqueuse
US44673099A Continuation 1997-07-11 1999-12-27

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US20080220975A1 US20080220975A1 (en) 2008-09-11
US7842648B2 true US7842648B2 (en) 2010-11-30

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US (1) US7842648B2 (fr)
EP (1) EP1000545B1 (fr)
CN (1) CN1219437C (fr)
AR (1) AR043068A1 (fr)
AT (1) ATE234009T1 (fr)
AU (1) AU742672B2 (fr)
BR (1) BR9810558B1 (fr)
CA (1) CA2295732C (fr)
DE (1) DE69812108T2 (fr)
WO (1) WO1999002036A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6867607B2 (ja) 2016-07-13 2021-04-28 日産化学株式会社 水性懸濁状農薬組成物
CN113632796A (zh) * 2021-07-29 2021-11-12 安徽黑包公有害生物防控有限公司 一种高效混合悬浮型除草剂

Citations (9)

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Publication number Priority date Publication date Assignee Title
JPS5639077A (en) 1979-07-17 1981-04-14 Ici Australia Ltd Alkanecarboxylic acid derivatives* their synthesization and herbicidal composition containing them
JPS57203066A (en) 1981-06-08 1982-12-13 Nissan Chem Ind Ltd Phenoxypropionic acid glycidyl ester derivative, its preparation and herbicide
EP0103171A1 (fr) 1982-08-13 1984-03-21 Nissan Chemical Industries Ltd. Concentré en forme de suspension pour la lutte contre les mauvaises herbes
US4629493A (en) 1979-02-22 1986-12-16 Nissan Chemical Industries Ltd. Heterocyclic ether type phenoxy fatty acid derivatives and herbicidal composition
JPH02214504A (ja) 1989-02-15 1990-08-27 Nissan Chem Ind Ltd 光学活性キノキサリン化合物の晶析法
JPH0753526A (ja) 1992-10-23 1995-02-28 Nippon Bayeragrochem Kk 除草性ピリミジニルチオアルカン誘導体
US5691276A (en) * 1994-06-23 1997-11-25 Nissan Chemical Corporation Herbicidal composition comprising a fluoropropylthiazoline sulfonylurea derivative and another herbicide
US6664213B1 (en) * 1999-08-19 2003-12-16 Nissan Chemical Industries, Ltd. Liquid pesticide composition
JP4076721B2 (ja) 1997-11-24 2008-04-16 エイチ． ウィルス、ロバート 分散型発電用耐単独運転方法および装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0476721A (ja) * 1990-07-18 1992-03-11 Canon Inc 情報入出力装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4629493A (en) 1979-02-22 1986-12-16 Nissan Chemical Industries Ltd. Heterocyclic ether type phenoxy fatty acid derivatives and herbicidal composition
JPS5639077A (en) 1979-07-17 1981-04-14 Ici Australia Ltd Alkanecarboxylic acid derivatives* their synthesization and herbicidal composition containing them
JPS57203066A (en) 1981-06-08 1982-12-13 Nissan Chem Ind Ltd Phenoxypropionic acid glycidyl ester derivative, its preparation and herbicide
EP0103171A1 (fr) 1982-08-13 1984-03-21 Nissan Chemical Industries Ltd. Concentré en forme de suspension pour la lutte contre les mauvaises herbes
JPH02214504A (ja) 1989-02-15 1990-08-27 Nissan Chem Ind Ltd 光学活性キノキサリン化合物の晶析法
JPH0753526A (ja) 1992-10-23 1995-02-28 Nippon Bayeragrochem Kk 除草性ピリミジニルチオアルカン誘導体
US5691276A (en) * 1994-06-23 1997-11-25 Nissan Chemical Corporation Herbicidal composition comprising a fluoropropylthiazoline sulfonylurea derivative and another herbicide
JP4076721B2 (ja) 1997-11-24 2008-04-16 エイチ． ウィルス、ロバート 分散型発電用耐単独運転方法および装置
US6664213B1 (en) * 1999-08-19 2003-12-16 Nissan Chemical Industries, Ltd. Liquid pesticide composition

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A. Shiroishi et al., Semi-batch cooling crystallization of quizalofop-ethyl with polymorphism, ACS Symp. Ser., (1990) 438 (Cryst. Sep. process), p. 261-270.
G. Sakata et al., Preparation of optically pure ethyl(R)-(+) and (S)-(-)-2[4-(6-Chloro-2-quinoxalinyloxy) phenoxy] propanoate by resolution method and their herbicidal activities, J. Pesticide Sci., (1985) 10(1) p. 75-79.
G. Sakata et al., Preparation of optically pure ethyl(R)-(+) and (S)-(−)-2[4-(6-Chloro-2-quinoxalinyloxy) phenoxy] propanoate by resolution method and their herbicidal activities, J. Pesticide Sci., (1985) 10(1) p. 75-79.
G. Sakata et al., Synthesis and herbicidal activity of optically active ethyl 2-[4-(6-chloro-2-quinoxalinyloxy) phenoxy] propanoate, J. Pesticide Sci., (1985) 10(1), p. 69-73.
K. Makino et al., Crystal structure of a new herbicide, ethyl 2-[4-(6-chloro-2-quinoxalinyloxy) phenoxy] propanoate, J. Pesticide Sci., (1986) 11(2), p. 237-243.
K. Miyake et al., Crystallization Behaviors of alpha- and beta-Quizalofop- ethyl Polymorphs in Homogeneous Nucleation, ACS Symp. Ser., (1997) 667 (Separation and purification by crystallization), p. 101-110.
K. Miyake et al., Crystallization Behaviors of α- and β-Quizalofop- ethyl Polymorphs in Homogeneous Nucleation, ACS Symp. Ser., (1997) 667 (Separation and purification by crystallization), p. 101-110.

Also Published As

Publication number Publication date
CA2295732C (fr) 2007-05-29
AU7550998A (en) 1999-02-08
AR043068A1 (es) 2005-07-20
CA2295732A1 (fr) 1999-01-21
AU742672B2 (en) 2002-01-10
BR9810558A (pt) 2000-08-15
DE69812108D1 (de) 2003-04-17
US20080220975A1 (en) 2008-09-11
DE69812108T2 (de) 2003-10-09
EP1000545B1 (fr) 2003-03-12
EP1000545A4 (fr) 2000-08-30
CN1263437A (zh) 2000-08-16
WO1999002036A1 (fr) 1999-01-21
BR9810558B1 (pt) 2011-10-18
ATE234009T1 (de) 2003-03-15
EP1000545A1 (fr) 2000-05-17
CN1219437C (zh) 2005-09-21

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